Metal Methanesulfonates with Mixed Anionic Groups with Large Band Gaps and Enhanced Birefringence

Mingli Liang; Yujie Zhang; Eugene Izvarin; Michael J. Waters; James M. Rondinelli; P. Shiv Halasyamani

doi:10.1021/acs.chemmater.3c03278

Metal Methanesulfonates with Mixed Anionic Groups with Large Band Gaps and Enhanced Birefringence

Mingli Liang, Yujie Zhang, Eugene Izvarin, Michael J. Waters, James M. Rondinelli, P. Shiv Halasyamani^*

^*Corresponding author for this work

Materials Science and Engineering

Research output: Contribution to journal › Article › peer-review

21 Scopus citations

Abstract

Four new metal methanesulfonates with mixed anionic groups, Bi(SeO₃)(CH₃SO₃) (1), Bi(TeO₃)(CH₃SO₃) (2), Ba(BF₄)(CH₃SO₃) (3), and Ba₂(BF₄)(CH₃SO₃)₃(H₂O)₃ (4), have been successfully synthesized. Compounds 1 and 2 are isomorphic and exhibit a two-dimensional (2D) layered structure. Stereoactive lone pairs are observed with Se⁴⁺, Te⁴⁺, and Bi³⁺. Compound 3 features a three-dimensional (3D) structure formed by connecting [Ba(CH₃SO₃)]⁺ layers via BF₄ tetrahedra, whereas compound 4 features a 2D layered structure, where the BF₄ tetrahedra are positioned on both sides of the [Ba₂(CH₃SO₃)₃]⁺ layers. The ultraviolet-visible-near-infrared (UV-vis-NIR) spectra indicate that compounds 1 and 2 have absorption edges at 270 and 274 nm, whereas compounds 3 and 4, with absorption edges below 200 nm, are characterized as deep-UV crystals. Calculations were performed to determine the absorption edges, and comparative analysis indicates a significant enhancement in the calculated birefringence values compared to analogous compounds.

Original language	English (US)
Pages (from-to)	2113-2123
Number of pages	11
Journal	Chemistry of Materials
Volume	36
Issue number	4
DOIs	https://doi.org/10.1021/acs.chemmater.3c03278
State	Published - Feb 27 2024

Funding

M.L., Y.Z., E.I., and P.S.H. thank the Welch Foundation (Grant E-1457) and the NSF (DMR – 2002319) for support. The computational work by M.J.W. and J.M.R. was supported by the National Science Foundation (NSF) Grant No. DMR-2011208 and they used resources of the National Energy Research Scientific Computing Center (NERSC), a U.S. DOE Office of Science User Facility located at Lawrence Berkeley National Laboratory, operated under Contract No. DE-AC02-05CH11231.

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering
Materials Chemistry

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10.1021/acs.chemmater.3c03278

Cite this

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title = "Metal Methanesulfonates with Mixed Anionic Groups with Large Band Gaps and Enhanced Birefringence",

abstract = "Four new metal methanesulfonates with mixed anionic groups, Bi(SeO3)(CH3SO3) (1), Bi(TeO3)(CH3SO3) (2), Ba(BF4)(CH3SO3) (3), and Ba2(BF4)(CH3SO3)3(H2O)3 (4), have been successfully synthesized. Compounds 1 and 2 are isomorphic and exhibit a two-dimensional (2D) layered structure. Stereoactive lone pairs are observed with Se4+, Te4+, and Bi3+. Compound 3 features a three-dimensional (3D) structure formed by connecting [Ba(CH3SO3)]+ layers via BF4 tetrahedra, whereas compound 4 features a 2D layered structure, where the BF4 tetrahedra are positioned on both sides of the [Ba2(CH3SO3)3]+ layers. The ultraviolet-visible-near-infrared (UV-vis-NIR) spectra indicate that compounds 1 and 2 have absorption edges at 270 and 274 nm, whereas compounds 3 and 4, with absorption edges below 200 nm, are characterized as deep-UV crystals. Calculations were performed to determine the absorption edges, and comparative analysis indicates a significant enhancement in the calculated birefringence values compared to analogous compounds.",

author = "Mingli Liang and Yujie Zhang and Eugene Izvarin and Waters, {Michael J.} and Rondinelli, {James M.} and Halasyamani, {P. Shiv}",

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year = "2024",

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doi = "10.1021/acs.chemmater.3c03278",

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T1 - Metal Methanesulfonates with Mixed Anionic Groups with Large Band Gaps and Enhanced Birefringence

AU - Liang, Mingli

AU - Zhang, Yujie

AU - Izvarin, Eugene

AU - Waters, Michael J.

AU - Rondinelli, James M.

AU - Halasyamani, P. Shiv

PY - 2024/2/27

Y1 - 2024/2/27

N2 - Four new metal methanesulfonates with mixed anionic groups, Bi(SeO3)(CH3SO3) (1), Bi(TeO3)(CH3SO3) (2), Ba(BF4)(CH3SO3) (3), and Ba2(BF4)(CH3SO3)3(H2O)3 (4), have been successfully synthesized. Compounds 1 and 2 are isomorphic and exhibit a two-dimensional (2D) layered structure. Stereoactive lone pairs are observed with Se4+, Te4+, and Bi3+. Compound 3 features a three-dimensional (3D) structure formed by connecting [Ba(CH3SO3)]+ layers via BF4 tetrahedra, whereas compound 4 features a 2D layered structure, where the BF4 tetrahedra are positioned on both sides of the [Ba2(CH3SO3)3]+ layers. The ultraviolet-visible-near-infrared (UV-vis-NIR) spectra indicate that compounds 1 and 2 have absorption edges at 270 and 274 nm, whereas compounds 3 and 4, with absorption edges below 200 nm, are characterized as deep-UV crystals. Calculations were performed to determine the absorption edges, and comparative analysis indicates a significant enhancement in the calculated birefringence values compared to analogous compounds.

AB - Four new metal methanesulfonates with mixed anionic groups, Bi(SeO3)(CH3SO3) (1), Bi(TeO3)(CH3SO3) (2), Ba(BF4)(CH3SO3) (3), and Ba2(BF4)(CH3SO3)3(H2O)3 (4), have been successfully synthesized. Compounds 1 and 2 are isomorphic and exhibit a two-dimensional (2D) layered structure. Stereoactive lone pairs are observed with Se4+, Te4+, and Bi3+. Compound 3 features a three-dimensional (3D) structure formed by connecting [Ba(CH3SO3)]+ layers via BF4 tetrahedra, whereas compound 4 features a 2D layered structure, where the BF4 tetrahedra are positioned on both sides of the [Ba2(CH3SO3)3]+ layers. The ultraviolet-visible-near-infrared (UV-vis-NIR) spectra indicate that compounds 1 and 2 have absorption edges at 270 and 274 nm, whereas compounds 3 and 4, with absorption edges below 200 nm, are characterized as deep-UV crystals. Calculations were performed to determine the absorption edges, and comparative analysis indicates a significant enhancement in the calculated birefringence values compared to analogous compounds.

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Metal Methanesulfonates with Mixed Anionic Groups with Large Band Gaps and Enhanced Birefringence

Abstract

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CCDC 2308321: Experimental Crystal Structure Determination

CCDC 2308320: Experimental Crystal Structure Determination

CCDC 2308323: Experimental Crystal Structure Determination

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Metal Methanesulfonates with Mixed Anionic Groups with Large Band Gaps and Enhanced Birefringence

Abstract

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ASJC Scopus subject areas

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Datasets

CCDC 2308321: Experimental Crystal Structure Determination

CCDC 2308320: Experimental Crystal Structure Determination

CCDC 2308323: Experimental Crystal Structure Determination

Cite this